Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• the present invention relates to a glass fiber reinforced resin composition and a molded article comprising the glass fiber reinforced resin composition.
• the glass fiber includes E glass composition (SiO 2 in the range of 52.0 to 56.0% by mass and Al 2 O 3 in the range of 12.0 to 16.0% by mass with respect to the total amount of glass fiber, Glass fiber (E glass fiber) having the composition of MgO and CaO in the range of 20.0 to 25.0% by mass and the composition of 5.0 to 10.0% by mass and B 2 O 3 is the most. It is used for general purposes.
• S glass composition (SiO 2 in the range of 64.0 to 66.0% by mass with respect to the total amount of the glass fiber, 24.0 to There is known a glass fiber (S glass fiber) comprising Al 2 O 3 in the range of 26.0% by mass and a composition containing MgO in the range of 9.0 to 11.0% by mass.
• the S glass composition has a 1000 poise temperature (temperature at which the viscosity of the melt of the glass composition becomes 1000 poise (100 Pa ⁇ s)) and a liquidus temperature (temperature of the melt of the glass composition). The temperature at which crystal precipitation occurs first) is high, and the working temperature range expressed by the difference between these two temperatures (the temperature range suitable for the production of glass fibers) is narrow, and the production of S glass compositions is not always easy. The problem of not being known.
• Molded products made of glass fiber reinforced resin compositions are increasingly used in the housings of electronic devices such as smartphones and laptop computers. Since smartphones and notebook computers are often carried and thus exposed to impacts such as dropping, molded products made of glass fiber reinforced resin compositions have a tensile strength, bending strength and bending strength. In addition to the elastic modulus, high impact strength is required.
• the molded article made of the glass fiber reinforced resin composition containing the glass fiber described in Patent Document 1 is equivalent to or less than the molded article made of the glass fiber reinforced resin composition containing the E glass fiber in terms of impact strength. There is an inconvenience.
• the present invention eliminates such disadvantages and provides a glass fiber reinforced resin composition capable of realizing a molded article having high tensile strength, high bending strength, high flexural modulus, and high impact strength, and the glass fiber reinforced resin. It aims at providing the molded article which consists of a composition.
• the glass fiber reinforced resin composition of the present invention comprises a glass fiber in the range of 10 to 90% by mass and a resin in the range of 90 to 10% by mass with respect to the total amount of the glass fiber reinforced resin composition.
• a glass fiber reinforced resin composition comprising: a glass fiber comprising SiO 2 in the range of 57.0 to 60.0% by mass and 17.5 to 20.0% by mass of the total amount of glass fiber.
• Al 2 O 3 in the range, MgO in the range of 8.5 to 12.0% by mass, CaO in the range of 10.0 to 13.0% by mass, and 0.5 to 1.5% by mass.
• B 2 O 3 and a composition in which the total amount of SiO 2 , Al 2 O 3 , MgO and CaO is 98.0% by mass or more is provided.
• the glass fiber reinforced resin composition of the present invention realizes a molded product having high tensile strength, high bending strength, high bending elastic modulus, and high impact strength by containing glass fiber having the above composition. be able to.
• the glass fiber reinforced resin composition of the present invention In a molded article made of the composition, sufficient tensile strength, sufficient bending strength, sufficient bending elastic modulus and sufficient impact strength cannot be obtained.
• the glass fiber reinforced resin composition of the present invention has a glass fiber content of more than 90% by mass or a resin content of less than 10% by mass with respect to the total amount of the glass fiber reinforced resin composition, It becomes difficult to produce a molded article made of the glass fiber reinforced resin composition.
• the glass fiber reinforced resin composition of the present invention is in the range of 20 to 70% by mass from the viewpoint of achieving both the strength of the molded product and the ease of production of the molded product. It is preferable to contain a glass fiber in the range of 80 to 30% by mass, more preferably a glass fiber in the range of 25 to 60% by mass and a resin in the range of 75 to 40% by mass. Preferably, it contains glass fiber in the range of 30 to 50% by mass and resin in the range of 70 to 50% by mass.
• the tensile strength of the molded product made of the glass fiber reinforced resin composition cannot be sufficiently improved.
• the glass fibers 1000 poise temperature and the liquidus temperature when the content exceeds 60.0 mass% of SiO 2 to the total amount of the glass fiber is increased, the production of glass fibers is difficult.
• the content of SiO 2 with respect to the total amount of glass fiber is preferably in the range of 58.2 to 59.8% by mass, and more preferably in the range of 58.4 to 59.7% by mass. , 58.6 to 59.6% by mass is more preferable, 58.8 to 59.5% by mass is particularly preferable, and 58.9 to 59.4% by mass is preferable. Most preferred.
• the content of SiO 2 when the content of SiO 2 is in such a range, the high tensile strength, bending strength and bending elastic modulus of the molded article made of the glass fiber reinforced resin composition, and the ease of producing the glass fiber, Can be made compatible.
• the glass fiber contained in the glass fiber reinforced resin composition of the present invention when the content of Al 2 O 3 with respect to the total amount of glass fiber is less than 17.5% by mass, a molded article made of the glass fiber reinforced resin composition The tensile strength, bending strength and flexural modulus of the steel cannot be sufficiently improved.
• the content of Al 2 O 3 with respect to the total amount of the glass fiber exceeds 20.0% by mass, the liquidus temperature becomes high and the working temperature range becomes narrow, making it difficult to produce the glass fiber.
• the impact strength of the molded article which consists of a glass fiber reinforced resin composition cannot fully be improved.
• the content of Al 2 O 3 with respect to the total amount of glass fiber is preferably in the range of 18.0 to 19.5% by mass, more preferably in the range of 18.2 to 19.3% by mass. More preferably, it is in the range of 18.3 to 19.1% by mass, and further preferably in the range of 18.4 to 18.9% by mass.
• the molded article made of the glass fiber reinforced resin composition has high tensile strength, high bending strength, high bending elastic modulus, and high impact strength. And the ease of manufacturing the glass fiber can be achieved.
• the tensile strength of the molded article made of the glass fiber reinforced resin composition is less than 8.5% by mass with respect to the total amount of glass fiber.
• the bending strength and the flexural modulus cannot be sufficiently improved.
• the content of MgO in the glass fiber exceeds 12.0% by mass with respect to the total amount of glass fiber, the liquidus temperature becomes high, so that the working temperature range becomes narrow and it becomes difficult to produce the glass fiber.
• the content of MgO with respect to the total amount of glass fiber is preferably in the range of 8.8 to 11.5% by mass, more preferably in the range of 9.0 to 11.0% by mass, More preferably, it is in the range of 9.2 to 10.5% by mass, particularly preferably in the range of 9.3 to 10.2% by mass, and in the range of 9.4 to 9.9% by mass. Is most preferred.
• the content of MgO is in such a range, the high tensile strength, high flexural strength, high flexural modulus, and high impact strength of the molded product made of the glass fiber reinforced resin composition, It is possible to achieve both the ease of production of glass fiber.
• the glass fiber contained in the glass fiber reinforced resin composition of the present invention when the CaO content with respect to the total amount of glass fiber is less than 10.0% by mass, the liquidus temperature becomes high, so the working temperature range becomes narrow. It becomes difficult to produce glass fibers, and the impact strength of a molded article made of a glass fiber reinforced resin composition cannot be sufficiently improved.
• the content of CaO with respect to the total amount of the glass fiber exceeds 13.0% by mass, the tensile strength, bending strength and bending elastic modulus of the molded product made of the glass fiber reinforced resin composition are sufficiently improved. I can't let you.
• the content of CaO with respect to the total amount of glass fiber is preferably in the range of 10.3 to 12.5% by mass, more preferably in the range of 10.5 to 12.3% by mass, It is more preferably in the range of 10.7 to 12.1% by mass, particularly preferably in the range of 10.9 to 11.9% by mass, and in the range of 11.1 to 11.8% by mass. Is most preferred.
• the molded article made of the glass fiber reinforced resin composition has high tensile strength, high bending strength, high bending elastic modulus, and high impact strength. It is possible to achieve both the ease of production of glass fiber.
• the glass fibers contained in the glass fiber-reinforced resin composition of the present invention if the content of B 2 O 3 to the glass fibers the total amount is less than 0.5 mass%, the glass fibers in producing the glass fiber Cutting is likely to occur, and the production efficiency decreases.
• the content of B 2 O 3 with respect to the total amount of the glass fiber is more than 1.5% by mass, the tensile strength, bending strength and bending elastic modulus of the molded product made of the glass fiber reinforced resin composition are set. It cannot be improved sufficiently.
• the content of B 2 O 3 with respect to the total amount of glass fiber is preferably in the range of 0.5 to 1.2% by mass, and preferably in the range of 0.5 to 1.0% by mass. More preferred.
• the molded article made of the glass fiber reinforced resin composition has high tensile strength, bending strength, bending elastic modulus, and excellent glass fiber. It is possible to achieve both the ease of manufacturing.
• the total amount of SiO 2 , Al 2 O 3 , MgO and CaO with respect to the total amount of glass fiber is less than 98.0% by mass,
• the content of impurity components is relatively increased.
• the working temperature range becomes narrow and it becomes difficult to produce glass fibers, or the tensile strength, bending strength, flexural modulus, and impact strength of molded articles made of glass fiber reinforced resin compositions are sufficiently improved. I can't.
• the total amount of SiO 2 , Al 2 O 3 , MgO and CaO with respect to the total amount of glass fiber is preferably 98.0% by mass or more and less than 99.5% by mass, and 98.5% by mass or more and 99%. More preferably, it is less than 0.0 mass%.
• the molded article made of the glass fiber reinforced resin composition has high tensile strength, high bending strength, high bending. It is possible to achieve both the elastic modulus and the high impact strength and the ease of producing the glass fiber.
• the ratio of CaO content (mass%) to Al 2 O 3 content (mass%) is in the range of 0.50 to 0.72, and the content (mass%) of B 2 O 3 and the content of CaO relative to the content (mass%) of Al 2 O 3 ( Mass ratio) ((B 2 O 3 (mass%) ⁇ CaO (mass%)) / Al 2 O 3 (mass%)) is preferably in the range of 0.22 to 1.00.
• CaO (mass%) / Al 2 O 3 (mass%) is in the range of 0.55 to 0.67
• CaO (wt%) / Al 2 O (Mass%) in the range of 0.57 to 0.65
• (B 2 O 3 (wt%) ⁇ CaO (wt%)) / Al 2 O 3 (wt%) is from 0.27 to 0 More preferably, it is in the range of .65.
• the high tensile strength, the high bending strength, the high bending elastic modulus, and the high impact strength of the molded article made of the glass fiber reinforced resin composition can be made compatible with the excellent manufacturability of the glass fiber. Can do.
• glass fibers contained in the glass fiber-reinforced resin composition of the present invention may contain Na 2 O and K 2 O.
• Na 2 O and K 2 O are usually added to lower the viscosity of the glass to make it easier to melt, but since the strength and chemical resistance of the glass fiber decrease, Na 2 O and K 2 O with respect to the total amount of glass fiber.
• the total amount of is preferably in the range of 0.05 to 1.0% by mass.
• glass fibers contained in the glass fiber-reinforced resin composition of the present invention may contain Fe 2 O 3.
• Fe 2 O 3 is usually present as an impurity in the glass raw material, it affects the absorption of radiant heat in the molten glass and the coloration of the glass fiber, so the content of Fe 2 O 3 with respect to the total amount of glass fiber is 0.05. It is preferably in the range of -1.0% by mass.
• the glass fibers contained in the glass fiber-reinforced resin composition of the present invention Na 2 O, if it contains K 2 O and Fe 2 O 3, Na 2 O with respect to glass fibers the total amount, K 2 O and Fe 2 O 3
• the total amount of is preferably in the range of 0.1 to 2.0 mass%, more preferably in the range of 0.1 to 0.5 mass%.
• the measurement of the content rate of each component mentioned above can be performed using an ICP emission spectroscopic analyzer for B which is a light element. These elements can be performed using a wavelength dispersive X-ray fluorescence analyzer.
• a glass fiber reinforced resin composition or a molded article made of a glass fiber reinforced resin composition is heated in a muffle furnace at 300 to 650 ° C. for about 0.5 to 24 hours, for example. Decompose organic matter.
• the remaining glass fiber is put in a platinum crucible, and is melted while being stirred in an electric furnace at a temperature of 1550 ° C. for 6 hours to obtain a homogeneous molten glass.
• the glass cullet is pulverized and powdered.
• the glass powder is alkali-melted and decomposed and then quantitatively analyzed using an ICP emission spectroscopic analyzer.
• Other elements are quantitatively analyzed using a wavelength dispersive X-ray fluorescence analyzer after glass powder is formed into a disk shape by a press. These quantitative analysis results are converted into oxides to calculate the content and total amount of each component, and the content of each component described above can be obtained from these numerical values.
• the glass fiber contained in the glass fiber reinforced resin composition has a ratio of the major axis to the minor axis of the sectional shape (major axis / minor axis) in the range of 2.0 to 10.0, and the cross-sectional area is a perfect circle. It is preferable to have a flat cross section having a fiber diameter (hereinafter also referred to as a converted fiber diameter) in the range of 3.0 to 35.0 ⁇ m when converted to.
• a converted fiber diameter fiber diameter
• the glass fiber reinforced when E glass fiber is used under the same conditions except for the composition as compared with the case where the glass fiber has a circular cross section.
• the improvement rate of the tensile strength, bending strength, bending elastic modulus, and impact strength based on the tensile strength, bending strength, bending elastic modulus, and impact strength of the molded product made of the resin composition is extremely high.
• the ratio of the major axis to the minor axis of the cross-sectional shape is high tensile strength, bending strength, bending elastic modulus, and impact strength of the molded article made of the glass fiber reinforced resin composition. From the viewpoint of compatibility with the ease of production of the fiber, it is preferably in the range of 2.2 to 6.0, and more preferably in the range of 3.2 to 4.5.
• the cross-sectional shape of the glass fiber means the cross-sectional shape of the glass filament forming the glass fiber.
• the converted fiber diameter refers to the high tensile strength, high bending strength, high bending elastic modulus, and high impact strength of the molded article made of the glass fiber reinforced resin composition, and the glass fiber or glass fiber reinforced resin composition. From the viewpoint of achieving both ease of manufacture when manufacturing the product, the range of 6.0 to 20 ⁇ m is preferable, and the range of 6.5 to 16.0 ⁇ m is more preferable.
• the fiber diameter of the glass fiber means the fiber diameter of the glass filament forming the glass fiber.
• the fiber diameter can range from 3.0 to 35.0 ⁇ m.
• the shape of the flat cross section is excellent in fluidity when producing a molded product from the glass fiber reinforced resin composition, so that it has a bowl shape, an oval shape or an oval shape (semicircles at both ends of the rectangle).
• a shape having a shape of a shape or a shape similar to that is preferred), and an oval shape is more preferred.
• the glass fiber contained in the glass fiber reinforced resin composition is preferably coated with a urethane resin, an epoxy resin, or a mixture of these resins.
• a urethane resin, an epoxy resin, or a mixture of these resins By covering the glass fiber with these, the adhesion between the glass fiber and the resin is increased, and the molded article made of the glass fiber reinforced resin composition has high tensile strength, high bending strength, high bending elastic modulus, and high impact. Strength is realized.
• the glass fiber is coated with a urethane resin, an epoxy resin, or a mixture of these resins, the glass fiber is coated with a component other than these resins in addition to these resins. Also good.
• a urethane resin, an epoxy resin, or a mixture of these resins is a glass fiber at a ratio of 0.1 to 1.0% by mass based on the mass of the glass fiber not coated with the resin. It is preferable to coat. By covering the glass fiber with a urethane resin, an epoxy resin, or a mixture of these resins within this range, the adhesiveness between the glass fiber and the resin can be reliably increased.
• the molded product of the present invention is composed of the glass fiber reinforced resin composition of the present invention described above. More specifically, the molded article of the present invention is obtained by subjecting the glass fiber reinforced resin composition of the present invention to an injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method, a foam molding method (also a supercritical fluid).
• Insert molding method in-mold coating molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, blow molding method, stamping molding method, infusion method, hand It is obtained by molding by a known molding method such as a lay-up method, a spray-up method, a resin transfer molding method, a sheet molding compound method, a bulk molding compound method, a pultrusion method, or a filament winding method.
• a known molding method such as a lay-up method, a spray-up method, a resin transfer molding method, a sheet molding compound method, a bulk molding compound method, a pultrusion method, or a filament winding method.
• the glass fiber reinforced resin composition of the present embodiment contains glass fibers in the range of 10 to 90% by mass and resin in the range of 10 to 90% by mass with respect to the total amount of the glass fiber reinforced resin composition.
• the fiber is composed of SiO 2 in the range of 57.0 to 60.0% by mass, Al 2 O 3 in the range of 17.5 to 20.0% by mass, and 8.5 to 12.0% by mass with respect to the total amount of glass fiber.
• the composition whose total amount of MgO and CaO is 98.0 mass% or more is provided.
• the glass fiber has a composition in the above range, a high tensile strength, a high bending strength, a high bending elastic modulus, and a high impact strength of a molded article made of the glass fiber reinforced resin composition are realized.
• the glass fiber provided with the said range is not limited to the reinforcing material of the molded article which consists of a resin composition, It can use suitably also as a reinforcing material of inorganic materials, such as a gypsum and cement.
• a glass fiber having the above-described range has a high melting temperature and a high softening temperature, and is excellent in heat resistance. Therefore, it can be particularly suitably used as a reinforcing material for inorganic materials that require high fire resistance.
• the glass fiber having the above range when used as a reinforcing material for gypsum (especially gypsum board having a thickness of 4 to 60 mm), is 0.1 to 4.0% by mass relative to the total mass of gypsum. It can be included in a range, and can contribute to improvement in mechanical strength, fire resistance, dimensional stability, etc. of gypsum. In the gypsum, the glass fiber having the above range may exist with a number average fiber length of 30 to 25000 ⁇ m.
• the glass fiber is manufactured by the following method. First, a glass raw material (glass batch) prepared to have the above composition is supplied to a melting furnace and melted at a temperature in the range of 1450 to 1550 ° C., for example. Next, the molten glass melted is discharged from a nozzle tip of a bushing controlled at a predetermined temperature, cooled while being stretched by winding at a high speed, and solidified to form glass fibers.
• the glass fiber is usually formed in a state where a plurality of glass filaments (for example, 50 to 8000) drawn from one nozzle chip are bundled. In general, the glass fiber has a circular cross section.
• the nozzle tip has a ratio of a major axis to a minor axis (major axis / minor axis) of 2.0 to 10.
• An opening (orifice hole) having a major axis of 1.0 to 10.0 mm and a minor axis of 0.5 to 2.0 mm in the range of 0, and a notch for rapidly cooling the molten glass that has passed through the opening A thing provided with cooling means, such as a section and a projection, can be used.
• the glass fiber has a weight in the range of 100 to 10,000 tex (g / km) by focusing a plurality of glass filaments.
• the glass fiber is improved in filament convergence, improved adhesion between the glass fiber and the resin, and improved in the uniform dispersibility of the glass fiber in the mixture of the glass fiber and the resin or the inorganic material.
• the surface is coated with an organic substance.
• organic substances include urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid-modified polypropylene), (poly) carboxylic acid (especially maleic acid) and co-polymerization of unsaturated monomers.
• a coalescence etc. can be mentioned, A urethane resin, an epoxy resin, or a mixture of these resins can be used preferably.
• a resin composition containing a silane coupling agent, a lubricant, a surfactant and the like can be used.
• Such a resin composition covers the glass fiber at a ratio of 0.1 to 2.0% by mass based on the mass of the glass fiber not coated with the resin composition.
• the coating of the glass fiber with the organic substance is performed by, for example, applying a resin solution or a resin composition solution to the glass fiber using a known method such as a roller type applicator in the glass fiber manufacturing process, and then the resin solution or the resin. It can carry out by drying the glass fiber to which the composition solution was provided.
• examples of the silane coupling agent include aminosilane ( ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) -N′- ⁇ .
• Lubricants include modified silicone oils, animal oils (beef tallow, etc.) and their hydrogenated products, vegetable oils (soybean oil, palm oil, rapeseed oil, palm oil, castor oil, etc.) and their hydrogenated products, animal waxes (beeswax, lanolin) Etc.), vegetable waxes (candelilla wax, carnauba wax, etc.), mineral waxes (paraffin wax, montan wax, etc.), condensates of higher saturated fatty acids and higher saturated alcohols (stearic acid esters such as lauryl stearate), Polyethyleneimine, polyalkylpolyamine alkylamide derivatives, fatty acid amides (for example, dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid) etc , Quaternary ammonium salt (
• surfactant examples include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. These can be used alone or in combination of two or more.
• Nonionic surfactants include ethylene oxide propylene oxide alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene-block copolymer, alkyl polyoxyethylene-polyoxypropylene-block copolymer ether, polyoxyethylene resin acid Ester, Polyoxyethylene fatty acid monoester, Polyoxyethylene fatty acid diester, Polyoxyethylene sorbitan fatty acid ester, Glycerol fatty acid ester ethylene oxide adduct, Polyoxyethylene caster oil ether, Hardened castor oil ethylene oxide adduct, Alkylamine ethylene oxide addition , Fatty acid amide ethylene oxide adduct, glycerol fatty acid ester, polyglyceride Fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide
• Cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (such as acetate and hydrochloride), ethylene oxide adducts to higher alkylamines, higher Examples include condensates of fatty acids and polyalkylene polyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkyl pyridinium salts.
• Anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, ⁇ -olefin sulfates, alkyl benzene sulfonates, ⁇ -olefin sulfonates, reaction of fatty acid halides with N-methyl taurine.
• Examples thereof include products, dialkyl ester salts of sulfosuccinic acid, higher alcohol phosphate esters, and phosphate ester salts of higher alcohol ethylene oxide adducts.
• amphoteric surfactants include amino acid-type amphoteric surfactants such as alkylaminopropionic acid alkali metal salts, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.
• thermoplastic resin a thermoplastic resin or a thermosetting resin can be used, but since there are many uses that require high tensile strength, high bending strength, high bending elastic modulus, and high impact strength, the thermoplastic resin. Is preferably used.
• thermoplastic resin examples include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / Acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polychlorinated Vinylidene (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene
• polyethylene examples include general-purpose polystyrene (GPPS), high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultrahigh molecular weight polyethylene.
• GPPS general-purpose polystyrene
• HDPE high-density polyethylene
• LDPE low-density polyethylene
• LLDPE linear low-density polyethylene
• ultrahigh molecular weight polyethylene ultrahigh molecular weight polyethylene.
• polypropylene examples include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.
• polystyrene examples include general-purpose polystyrene (GPPS), which is an atactic polystyrene having an atactic structure, impact-resistant polystyrene (HIPS) obtained by adding a rubber component to GPPS, and syndiotactic polystyrene having a syndiotactic structure.
• GPPS general-purpose polystyrene
• HIPS impact-resistant polystyrene
• methacrylic resin one kind of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, fatty acid vinyl ester is homopolymerized or two or more kinds are copolymerized.
• a polymer is mentioned.
• Polyvinyl chloride can be copolymerized with a vinyl chloride homopolymer or a vinyl chloride monomer polymerized by a conventionally known emulsion polymerization method, suspension polymerization method, micro suspension polymerization method, bulk polymerization method or the like. Examples thereof include a copolymer with a monomer, and a graft copolymer obtained by graft-polymerizing a vinyl chloride monomer to a polymer.
• Polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebamide (nylon 410) polypentamethylene adipamide (Nylon 56), polypentamethylene sebamide (nylon 510), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), polydeca Methylene sebacamide (nylon 1010), polydecane methylene dodecane (nylon 1012), polyundecanamide (nylon 11), polyundecane methylene adipamide (nylon 116), polydodecanamide (nylon 12), polyxylene azide Pa (Nylon XD6), polyxylene sebamide (nylon XD10), polymetaxylylene adipamide (nylon MXD6), polyparaxylylene a
• the polyacetal includes a homopolymer having an oxymethylene unit as a main repeating unit, and a copolymer mainly comprising an oxymethylene unit and having an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain. Is mentioned.
• polyethylene terephthalate examples include a polymer obtained by polycondensation of terephthalic acid or a derivative thereof and ethylene glycol.
• polybutylene terephthalate examples include a polymer obtained by polycondensation of terephthalic acid or a derivative thereof and 1,4-butanediol.
• polytrimethylene terephthalate examples include a polymer obtained by polycondensation of terephthalic acid or a derivative thereof and 1,3-propanediol.
• polycarbonate examples include a polymer obtained by a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted in a molten state, or a polymer obtained by a phosgene method in which a dihydroxyaryl compound and phosgene are reacted. It is done.
• polyarylene sulfide examples include linear polyphenylene sulfide, cross-linked polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ether, polyphenylene sulfide ketone and the like that have been polymerized by performing a curing reaction after polymerization.
• Modified polyphenylene ethers include polymer alloys of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, and poly (2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene copolymers.
• polyaryl ketone examples include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).
• PEK polyether ketone
• PEEK polyether ether ketone
• PEKK polyether ketone ketone
• PEEKK polyether ether ketone ketone
• the liquid crystal polymer (LCP) includes at least one structural unit selected from an aromatic hydroxycarbonyl unit, an aromatic dihydroxy unit, an aromatic dicarbonyl unit, an aliphatic dihydroxy unit, an aliphatic dicarbonyl unit, and the like, which are thermotropic liquid crystal polyesters.
• (Co) polymers consisting of
• Fluorine resins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyfluorinated Examples include vinylidene (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy resin
• FEP fluorinated ethylene propylene resin
• ETFE fluorinated ethylene tetrafluoroethylene resin
• PVDF polyvinyl fluoride
• PCTFE polychlorotrifluoroethylene
• ECTFE ethylene / chlorotrifluoroethylene resin
• ionomer (IO) resin examples include a copolymer of an olefin or styrene and an unsaturated carboxylic acid, in which a carboxyl group is partially neutralized with a metal ion.
• olefin / vinyl alcohol resin examples include ethylene / vinyl alcohol copolymer, propylene / vinyl alcohol copolymer, saponified ethylene / vinyl acetate copolymer, saponified propylene / vinyl acetate copolymer, and the like.
• cyclic olefin resin examples include monocyclic substances such as cyclohexene, polycyclic substances such as tetracyclopentadiene, and polymers of cyclic olefin monomers.
• polylactic acid examples include poly-L-lactic acid, which is an L-form homopolymer, poly-D-lactic acid, which is a D-form homopolymer, or stereocomplex polylactic acid, which is a mixture thereof.
• cellulose resin examples include methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.
• thermosetting resin examples include unsaturated polyester resin, vinyl ester resin, epoxy (EP) resin, melamine (MF) resin, phenol resin (PF), urethane resin (PU), polyisocyanate, polyisocyanurate, Polyimide (PI), urea (UF) resin, silicon (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleidotriazine (BT) resin, diallyl phthalate resin (PDAP), etc. Can be mentioned.
• examples of the unsaturated polyester include resins obtained by esterifying a carboxylic acid and an aliphatic diol when aliphatic unsaturated.
• vinyl ester resin examples include bis vinyl ester resin and novolac vinyl ester resin.
• Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 '-(1,3-phenylenediisopridiene) ) Bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 ′-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4′-cyclohexyldiene bisphenol) Type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, novolak type epoxy resin having condensed ring aromatic hydrocarbon structure, biphenyl type epoxy Fatty, aralkyl epoxy resins such as xylylene type epoxy resins and phenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthol type epoxy resins, naphthalene diol type
• melamine resin examples include a polymer formed by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.
• phenol resin examples include phenol novolac resins, cresol novolac resins, bisphenol A type novolak resins and other novolak type phenol resins, methylol type resole resins, dimethylene ether type resole resins and the like resol type phenol resins, or aryl alkylene type phenol resins. Among them, one of them or a combination of two or more thereof can be mentioned.
• urea resins examples include resins obtained by condensation of urea and formaldehyde.
• thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more.
• the glass fiber reinforced resin composition of the present invention can contain components other than the glass fiber and the resin as long as the object of the present invention is not impaired.
• glass fibers other than the glass fibers for example, E glass fibers, S glass fibers
• reinforcing fibers other than glass fibers for example, carbon fibers, metal fibers
• fillers other than glass fibers for example, , Glass powder, talc, mica
• flame retardant for example, UV absorber, heat stabilizer, antioxidant, antistatic agent, fluidity improver, antiblocking agent, lubricant, nucleating agent, antibacterial agent, pigment, etc.
• the glass fiber reinforced resin composition of the present invention can contain these components in a total range of 0 to 40% by mass with respect to the total amount of the glass fiber reinforced resin composition.
• the glass fiber reinforced resin composition of the present invention is obtained, for example, by kneading glass fibers (chopped strands) formed by converging a plurality of glass filaments and cut to a length of 1 to 25 mm with a resin. be able to.
• the obtained glass fiber reinforced resin composition can be processed into a pellet shape by extrusion from a nozzle and cutting into a predetermined length (for example, 1 to 50 mm).
• the glass fiber reinforced resin composition of the present invention is formed by impregnating a molten thermoplastic resin into glass fibers (rovings) formed by concentrating a plurality of glass filaments and continuously wound. By cooling, it can be obtained by holding the thermoplastic resin around the roving.
• the obtained glass fiber reinforced resin composition can be processed into a pellet shape by cutting into a predetermined length (for example, 1 to 50 mm).
• a predetermined length for example, 1 to 50 mm.
• the fiber length of the glass fiber in the glass fiber reinforced resin composition is substantially equal to the length of the pellet (predetermined cut length).
• the molded product made of the glass fiber reinforced resin composition of the present invention can be obtained, for example, by processing the pellets obtained as described above into a molded product by the known molding method described above.
• the number average fiber length of the glass fiber in the molded product is, for example, in the range of 250 to 400 ⁇ m, and 265 A range of ⁇ 350 ⁇ m is preferable.
• the glass fiber reinforced resin composition the glass fiber has an average fiber length in the above range, so that a high tensile strength, a high bending strength, a high bending elastic modulus of a molded article made of the glass fiber reinforced resin composition, And high impact strength is achieved.
• the ratio of the glass fibers having a fiber length of 250 ⁇ m or more is 40.0. It is preferably at least 4% by mass, more preferably at least 45.0% by mass, and even more preferably at least 48.0% by mass.
• the fiber length of the glass fiber is distributed in this way, so that the molded product composed of the glass fiber reinforced resin composition has high tensile strength, high bending strength, High flexural modulus and high impact strength are achieved.
• a molded article comprising the glass fiber reinforced resin composition is, for example, 300 to 650 ° C.
• Organic matter is decomposed by heating in a muffle furnace for about 0.5 to 24 hours.
• the remaining glass fibers are transferred to a glass petri dish and dispersed on the petri dish surface using acetone.
• the fiber length is measured using a stereomicroscope for 500 or more glass fibers dispersed on the surface, and the number average fiber length is calculated.
• Examples of the uses of the molded article made of the glass fiber reinforced resin composition of the present invention include electronic equipment casings, electronic parts, vehicle exterior members (bumpers, fenders, bonnets, air dams, wheel covers, etc.), vehicle interior members (door trim , Ceiling materials, etc.), vehicle engine surrounding members (oil pan, engine cover, intake manifold, exhaust manifold, etc.), muffler related members (silencer member, etc.), high pressure tanks, and the like. Since it is required to have a high level of tensile strength, flexural strength, flexural modulus, and impact strength, smartphones, tablets, and notebook computers can be used as molded products made of the glass fiber reinforced resin composition of the present invention.
• Portable electronic device housings such as portable music players and portable game machines are preferred.
• compositions shown in Table 1 Four types of glass compositions shown in Table 1 were used.
• composition 1 and composition 2 are glass compositions of glass fibers used in the glass fiber reinforced resin composition of the present invention
• composition 3 is glass fiber reinforced resin of the present invention in which Al 2 O 3 , CaO and B 2 O 3 are used.
• the glass fiber used in the composition is out of the range of the glass composition, and the composition 4 corresponds to the E glass composition.
• the fiber elastic modulus of each glass composition is obtained by adhering a single glass filament free from scratches, deterioration, etc. due to contact, friction, etc., to a predetermined mount having a hole with a diameter of 50 mm in the center to obtain a test piece.
• the test piece was set on the gripping tool of the tensile tester, and after the end of the mount was cut, a tensile test was conducted at a crosshead speed of 5 mm / min, and the initial strength fluctuation value and the elongation corresponding thereto were calculated.
• Panlite L-1250Y (trade name, manufactured by Teijin Ltd.) was used as the polycarbonate (indicated as PC in the table).
• the Charpy impact strength composed of the glass fiber reinforced resin composition was measured according to ISO179.
• Example 1-2 Comparative example 1-2
• Table 2 the glass fiber reinforced resin composition comprising a glass fiber having a circular cross section with each of the compositions 1 to 4 and polyamide, and the case where the glass fiber has the composition 1 is described in Example 1.
• Example 2 is provided with Example 2
• Comparative Example 1 is provided with Composition 3
• Comparative Example 2 is provided with Composition 4
• the tensile strength, bending strength, and molded product made of the glass fiber reinforced resin composition are as follows. Flexural modulus and Charpy impact strength were evaluated.
• the numerical values in square brackets in the columns of tensile strength, bending strength, flexural modulus and Charpy impact strength mean relative values when the composition 4 (E glass composition) is used as 100. .
• the molded article made of the glass fiber reinforced resin composition of Example 1 and Example 2 having the glass composition defined in the present invention is the glass fiber reinforced resin of Comparative Example 2 having the E glass composition.
• all of the tensile strength, bending strength, flexural modulus, and Charpy impact strength are high values.
• a molded article made of the glass fiber reinforced resin composition of Comparative Example 1 in which Al 2 O 3 , CaO and B 2 O 3 are out of the range of the glass composition defined in the present invention has a tensile strength, a bending strength and The flexural modulus is higher than those of Examples 1 and 2 and Comparative Example 2, but the Charpy impact strength is inferior to that of Comparative Example 2.
• Example 3-4 Comparative Example 3-4
• Table 3 As shown in Table 3, with respect to a glass fiber reinforced resin composition comprising a glass fiber having an oval cross-section each having the compositions 1 to 4 and polyamide, a case where the glass fiber has the composition 1 is described in Example 3.
• the case where the composition 2 is provided is Example 4
• the case where the composition 3 is provided is Comparative Example 3
• the case where the composition 4 is provided is Comparative Example 4
• the tensile strength and bending strength of the molded article made of the glass fiber reinforced resin composition The flexural modulus and Charpy impact strength were evaluated.
• the numerical values in square brackets in the columns of tensile strength, bending strength, flexural modulus and Charpy impact strength mean relative values when the composition 4 (E glass composition) is used as 100. .
• the molded article made of the glass fiber reinforced resin composition of Example 3 and Example 4 having the glass composition defined in the present invention is the glass fiber reinforced resin of Comparative Example 4 having the E glass composition.
• the cross-sectional shape of the glass fiber is a flat cross section (oval)
• a molded product made of a glass fiber reinforced resin composition containing glass fiber having an E glass composition was used as a reference. The improvement rate of tensile strength and the like is extremely high.
• a molded article made of the glass fiber reinforced resin composition of Comparative Example 3 in which Al 2 O 3 , CaO and B 2 O 3 are out of the range of the glass composition defined in the present invention has a tensile strength, a bending strength and Although the flexural modulus is higher than that of Comparative Example 4, the Charpy impact strength is equivalent to that of Comparative Example 4.
• Example 5 Comparative Example 5-6
• Table 4 As shown in Table 4, with respect to a glass fiber reinforced resin composition composed of a glass fiber having an oval cross section having each of the compositions 2 to 4 and polycarbonate, a case where the glass fiber has the composition 2 is described in Example 5, The case where the composition 3 is provided is Comparative Example 5 and the case where the composition 4 is provided is Comparative Example 6, and the tensile strength, bending strength, bending elastic modulus and Charpy impact strength of the molded article made of the glass fiber reinforced resin composition are evaluated. did.
• the molded article made of the glass fiber reinforced resin composition of Example 2 having the glass composition defined in the present invention is made of the glass fiber reinforced resin composition of Comparative Example 6 having the E glass composition. Compared to the molded product, all of tensile strength, bending strength, flexural modulus, and Charpy impact strength are high values.
• a molded article made of the glass fiber reinforced resin composition of Comparative Example 5 in which Al 2 O 3 , CaO and B 2 O 3 are out of the range of the glass composition defined in the present invention has tensile strength, bending strength and The flexural modulus is higher than that of Comparative Example 6, but the Charpy impact strength is inferior to that of Comparative Example 6.

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• 2016
  • 2016-09-05 JP JP2016173212A patent/JP6702099B2/ja active Active
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